Substituted thiuram polysulphide and process of making



v 35 are represented by the generalformula:

Paamafm; 4 1930' .I-AUNITED STATES.

LO F GE" GEORGE STAFFORD WHITBY, or MONTREAL, 'aunsnc, oaN-ADLYAssiGNoRfBY MESNE ASSIGNMENTS, Torrie ROESSLER 8a HASSLACHER c 1vrrc L coivrr Nmor NEW YORK, N. Y., A CORPORATION or DELAWARE V ilarly this invention relates to the products formed by treating the salts of substituted dithiocarbamic acids with sulphur monochloride or sulphur dichloride. I have found that the substancesso formed may be used as ac- 10 celerators of the vulcanization of rubber;

. This use is claimed by me in a co-pending ap- V plication S. N. 84,154 filed by me of even date herewith. This application is a continuation in part of my application S. N. 84,153. Throughout the specification Irefer to specific sulphur chlorides as sulphur monochloride and sulphur dichloride giving formulas corresponding respectively to S 01 and S61 I do not wish to be limited in this since there is some doubt as to the existence or structure of the dichloride. HowevemI have found that by using the commonly called dichloride I obtain a definite compound of the same class as, but differing from, the product obtained by using the monochloride. Furthermore, sulphur is very soluble in these 5 sulphur chlorides and may be prese'nt'in mol- H ecules of a polysulphide nature having sev eral loosely bound S atoms in addition to 0 those ascribed to them by the formulae. I

therefore prefer to express the sulphurjchlorides above referred to as S Cl wherein w represents a whole number other than zero The dithiocarbamates used in my processes wherein R and R are any similar or dissimi- 4 larorganic radicals, and M is any metallic in' case a piperidyl or any other bivalent radical is used, It and R will become a single raclicalutilizing the double bond, but the dithiocarbamate will still be considered disubstituted.

I 'have discovered that if such a salt is SUBSTITUTED mniunaivr roii swirmnn AND rRoc ss or MAKING 192s; Seria1 No. 273 ,777.

treated with afsulphurl ehloride a reaction 7 takes place between two moles oft-he dithiocarbamate and one inol'e ofthesulphur I chloride to form a new composition of niatter,

follows:

Substantially, I believe this reaction tobe as represent asfollowsz i The ammonium chloride or, as the-case may be, themetal chloride is always formed at the end of the reaction. The arrangement of the central sulphuratoms-represented as S S or S 111' unknown to me; I have, however,"

found that definiteicompositions are always formed as is shown by the properties of the various products. The products are simply named as substituted thiurampolysulphides', I have 'preparedanalogous materials fronii several dithiocarbamates, and find the reaction similar in all cases. i I have employed the v dimethyl diethyl-, piperidyL, phenylunethyh, phenyl ethyl-, dithiocarbamates; I have used'zinc, sodium variety of liquids. I have found suitable media to be benzene, petroleum ether or sulphuric ether.

dibutyl diprop'yL, I

potassium'and ammonium salts of these'in a Example The following example willserve to illustrate the method of preparation that I have used: I

205 gms. powdered potassium dimethyldithiocarbainate was suspended in about 250 cos. ether, cooled well with ice. While stir- I ring vigorously by mechanical means, 8.?

gms. sulphur monochloride diluted with petroleum ether was gradually run in. The precipitate was filtered, washed with ether, and allowed todry. This was powdered, suspended in water, filtered, washed with water, dried by suction,and finallyallowed to dry completely in the air. Yield: 12.35

gmsofa cream colored powder. M.P.: about 108 (it turned yellow at 75; shrunk softenedat 100), Yield: 64%.

Claims 1. The method of producing tetra alkyl polysulphides which comprises treating salts of dialkyl dithiocarbamic acid with sulphur chloride.

2. Process for the manufacture of a tetramethyl *thiuram polysulphide which comprises reacting a salt of dimethyl dithio-' carbamic acid with a chloride of sulphur. 3. Process for the'manufacture of tetramethyl thiuram tetrasulphide which comprises reacting a salt of dimethyl dithiocarbainic acid with sulphur monochloride.

4. Process for the manufacture oftetramethyl thiuram tetrasulphide which comprises reacting sodium dimethyl dithiocarbamate with sulphur monochloride.

5. A composition of matter comprising a tetra alkyl thiuram tetrasulphide.

6. A composition of matter comprising tetra-methyl 'thiuram polysulphide of the general formula (Me l T.()S) S where w is any whole number.

7. A composition of matter comprising tetra methyl-thiuram tetrasulphideQ Signed at Montreal, Quebec, Canada, this twelfth day of March, A. D. 1920.

' GEORGE STAFFORD WHITBY.

at 92, 7 V 

